Luminescent device having rare earth-doped silica glass luminescent material

ABSTRACT

This disclosure relates to a luminescent device having a uniformly coalesced, transparent, luminescent silica glass target containing an activating amount of at least one selected rare earth oxide. This disclosure further relates to a luminescent process, a composition, and an article of manufacture.

United States Patent Inventors Stephen W. Barber Toledo, Ohio;

William F. Nelson, Port Washington, N.Y. 41,455

May 28, 1970 Jan. 1 l 1972 Owens-Illinois, Inc.

Original application July 1, 1969, Ser. No. 841,690, now Patent No. 3,527,71 1, dated Sept. 8, I970. Divided and this application May 28, 1970, Ser. No. 41,455

Appl. No. Filed Patented Assignee LUMINESCENT DEVICE HAVING RARE EARTH- DOPED SILICA GLASS LUMINES CENT MATERIAL OTHER REFERENCES de Boisbaudran- Surguelques Nowvelles Fluorescence Comptes Rendus, Vol. CX, No. 1, pp. 24- 8 189.

Primary Examiner Robert D. Edmonds Attorneys- E. .I. Holler and C. S. Lynch ABSTRACT: This disclosure relates to a luminescent device having a uniformly coalesced, transparent, luminescent silica glass target containing an activating amount of at least one selected rare earth oxide. This disclosure further relates to a luminescent process, a composition, and an article of manufacture.

LUMINESCENT DEVICE HAVING RARE EARTH-DOPE!) SILICA GLASS LUMINESCENT MATERIAL RELATED APPLICATION THE INVENTION This invention relates to the preparation and use of novel glass compositions consisting essentially of silica and small effective amounts of at least one selected oxide ingredient.

More particularly, in accordance with this invention, a substantially transparent, uniformly coalesced, homogeneous glass is prepared by uniformly compacting a homogeneous, anhydrous mixture consisting essentially of finely divided, substantially pure, noncrystalline silica and a small effective amount of at least one glass-modifying oxide ingredient selected to impart desired characteristics to the glass, and then heating the compacted mixture under vacuum at an elevated, nondevitrifying temperaturefor a period of time sufficient to obtain substantially complete, uniform coalescence and sintering of the mixture.

A wide range of oxide ingredients maybe selected for the practice of this invention depending upon'the characteristics desired in the glass body.

Typical ingredients include not by way of limitation the oxides of V, Cr, Mn, Fe, Co, Ni, Cu, Sb, Zn, P. B,U, Ti, Zr, Hf, W, Ta, Ag, Au, Pb, Bi, As, and the rare earths.

In accordance with one important embodiment of this invention, it is contemplated preparing a novel, substantially transparent, homogeneous, luminescent glass having a luminescence output of high intensity by uniformly compacting a homogeneous, anhydrous mixture consisting essentially of finely divided, noncrystalline, substantially pure silica and a small effective amount of at least one luminescent oxide activator, and heating the compacted mixture under vacuum at an elevated, nondevitrifying temperature for a period of time sufficient to obtain substantially complete coalescence thereof.

A wide range of luminescent oxide activators or dopants is contemplated herein including not by way of limitation oxides of Sn, Sb, Zn, Ni, V, Mn, U, Cu, Ag, As, and the rare earths.

It has been discovered that compounds of the rare earths are particularly suitable for the practice of this invention. More particularly, it has been found that luminescent glasses of high-intensity output may be prepared by using one rare earth selected from lanthanum, cerium, praseodymium, neodymium, samarium, europium, gadolinium, terbium, dysprosium, erbium, thulium, ytterbium, and lutetium alone or in combination with at least one other rare earth selected from lanthanum, cerium, praseodymium, neodymium, samarium, europium, gadolinium, terbium, dysprosium, erbium, thulium, ytterbium, lutetium, and holmium.

Specific rare earth combinations contemplated herein include:

1. La and at least one member selected from Ce, Pr, Nd, Sm, Eu, Gd, Tb, Dy, Tm, Yb, and Lu.

2. Ce and at least one member selected from Pr, Nd, Sm, Eu, Gd, Tb, Dy, Ho, Er, Tm, Yb, and Lu.

3. Pr and at least one member selected from Nd, Sm, Eu, Gd, Tb, Dy, Ho, Er, Tm, Yb, and Lu.

4. Nd and at least one member selected from Sm, Eu, Gd, Tb, Dy, Ho, Er, Tm, Yb, and Lu.

5. Sm and at least one member selected Dy, l-lo, Er, Tm, Yb, and Lu.

6. Eu and at least one member selected from Gd, Tb, Dy, Ho, Er, Tm, Yb, and Lu.

7. Gd and at least one member selected from Tb, Dy, I-Io, Er, Tm, Yb, and Lu.

8. Tb and at least one member selected from Dy, I-Io, Er, Tm, Yb, and Lu.

9. Dy and at least one member selected from Ho, Er, Tm, Yb, and Lu. I

from Eu, Gd, Tb,

10. Ho and at least one member selected from Tm, Yb, and Lu.

1 L'Er and at least one member selected from Tm, Yb, and

Y Lu.

l2. Tm and at least one member selected from Yb and Lu.

l3. Yb and Lu.

In accordance with another embodiment of this invention, it is contemplated using a luminescent glass body (prepared by the novel process described hereinbefore) as the target material.

Luminescence is photon emission initiated by energy forms other than thermal agitation. Luminescence of a solid under excitation requires suitable arrangement and population of the electronic energy levels in its constituent atoms: properly situated electrons are excited to higher energy levels under excitation, and emit photons upon their spontaneous return to lower levels. Luminescent materials are used commercially in cathode-ray tubes, particularly television picture tubes, X-ray and radar screens, Oscilloscopes, electron microscopes, fluorescent lights, radiation detection devices, and luminous markers, signs, and dials.

Luminescence device herein means any apparatus or contrivance in which energizing radiation is converted to luminescence emission; target herein means the material, regardless of shape or form, in a luminescence device which effects this conversion. cathodoluminescence device and photoluminescence device refer, respectively, to luminescence devices in which the energizing agent is cathode rays or photon radiation. Most present commercial luminescence'devices use targets composed of polycrystalline phosphors prepared by sintering powdered inorganic reactants selected to provide the'necessary host and activator components. The resultant aggregates are ground or otherwise reduce to a particle size of about 1 to 20 microns, and then deposited on a substrate. Organic materials are often used as binders to obtain more uniform phosphor deposition, or as membrane coatings for the phosphor to provide a surface which can be aluminized. Several disadvantages attend these processes: comminution adversely affects luminescence effi ciency of the phosphors; the phosphors inherent sensitivity to deterioration by chemical attack is enhanced by their large surface/volume ratio when powdered; uniform contact among phosphor particles and with the substrate is difficult to achieve, and inadequate contact causes light scattering which decreases effective output; phosphor coatings have little abrasion resistance, and binders used in their preparation are subject to thermal deterioration; and, of course, product fabrication techniques are limited to those which do not adversely affect the sensitive phosphor screens. In cathodoluminescence devices the excitation current must be kept below levels, usually low, which damage the phosphor. Also, the screen is usually low, which damage the phosphor. Also, the screen is usually opaque, and consequently resolution and definition of a projected image are relatively poor. A known process designed to overcome some of these problems involves blending powdered phosphor in a frit, followed by fusion. The phosphor deteriorates under this treatment, however, and the inhomogeneity of the resultant glass causes objectionable scattering of emitted light.

The luminescence devices of the present invention overcome many of these disadvantages by employing a target comprising a glass body consisting essentially of silica and a metal or metalloid oxide wherein the oxide is preferably that of a rare earth element as described hereinbefore. Broadly, the glass body consists essentially of vitreous silica with small amounts of the aforesaid glass-modifying metal or metalloid oxide, e.g., at least one rare earth oxide, where the number of metal or metalloid atoms per million silicon atoms is from 5 to 5,000.

These compositions possess the unique and advantageous properties of vitreous silica, including high-chemical durability and low-thermal expansion with consequent resistance to thermal shock. The transparency of silica allows transmission of a greater range of exciting radiations than other glasses and most crystals. Its optical transparency in particular allows excellent resolution, definition, and contrast ratio, so that images remain visible at luminosity levels lower than those which are adequate with commercial opaque phosphors; conversely, the vitreous silica host can withstand extremely highcurrent density without damage, allowing cathodoluminescence to achieve high luminosity. The silica rare earth oxide glasses of this invention possess particularly unique and unexpectedly bright luminescence, especially cathodoluminescence, when excited as hereinafter described.

The vitreous silica rare earth oxide glass bodies used in the devices of the present invention are prepared by novel procedures which comprise a further aspect of this invention. Prior art methods for preparing vitreous silica and forming objects therefrom can be classified into those which begin with crystalline silica and those which use vitreous silica as a starting material. The formation of vitreous silica from one of its crystalline forms has been carried out by fusion and by sintering. The fusion process requires temperatures above 1,710 C., the liquidus of betacristobalite. The resultant melt is difficult to handle. It has a high viscosity which causes it to retain dissolved and entrapped gases tenaciously, a high-vapor pressure, and a strong affinity for impurities which enhance an already pronounced tendency to devitrify during cooling. For these reasons, properties such as transparency or homogeneity are often sacrificed to avoid the difficulties associated with prolonged high-temperature treatments, and the resultant products are allowed to retain partial crystalline character. Thus in the process described in U.S. Pat. No. 2,958,604, particulate crystalline silica (quartz) on which cerium oxide has been uniformly deposited is heated momentarily to 1,750 C. to obtain a fused product which resists darkening on exposure to nuclear radiation. Undoubtedly, the product retains substantial crystalline character, since it has been shown that to obtain truly vitreous silica in which all quartz structure is obliterated, crystalline starting material must be subjected to long exposure to temperatures of 1,800 to l,900 C.; see V. A. Florinskaya and R. S. Pechenkina, Dokl. Akad. Nauk SSSR 85, 1265 (1952). When optically transparent completely vitreous silica is to be prepared from crystalline precursors, fusion must be effected at prolonged high temperatures; a typical process requires temperatures near 1,850 C. for 8 hours under vacuum, to remove from the melt bubbles which otherwise provide sites for initiation of devitrification during cooling. Known sintering processes for converting crystalline silica to partially vitreous silica involve temperatures of about 1,ll to l,700 C. The higher temperatures in this range allow faster glass formation, but incur the problem of cristobalite crystallization, which occurs at 1,300 to 1,7 10 C. The difficulties involved in sintering quartz to obtain vitreous silica are discussed at length in U.S. Pat. No. 2,270,718.

Vitreous silica is available from sources other than its crystalline forms: particulate vitreous silica can be prepared by the hydrolysis or combustion of suitable silicon compounds such as silicon halides and organosilanes. The finely divided material thus obtained can be condensed directly upon a molten surface and immediately fused as described in U.S. Pat. Nos. 2,188,121 and 2,272,342. Particulate vitreous silica from these sources or that obtained by grinding fused silica can also be employed to form large vitreous bodies by slip-casting techniques which require firing at 1,l00 to 1,260 C. for about 1 to 4 hours. The products are translucent or opaque, porous, and partly crystalline; see J. D. Fleming, Am. Ceram. Soc. Bull., 40 (12), 748 (1961). A similar process at slightly higher temperatures (1,200 to l,450 C.) has been said to give transparent products (U.S. Pat. No. 2,268,589). Processes which begin with particulate vitreous silica but require temperatures well above the fusion point of betacristobalite are also known: British Pat. No. 524,442 (1940) specifies 1,800 to 2,l00 C.; S. D. Brown, The Devitrification of High-Temperature Glass (Thesis, University of Utah, 1957) suggests l,800 to 1,900 C. The difficulties expected from silica melts at these temperatures have already been noted.

We have now discovered a method for preparing homogeneous, optically transparent, vitreous silica bodies essentially devoid of crystalline structure and voids, at temperatures well below 1,800" C. In particular, we have discovered a method for preparing vitreous luminescent bodies which consist essentially of substantially pure, noncrystalline silica and a relatively lesser portion of at least one metal or metalloid oxide, especially a rare earth oxide.

Within the useful concentration range already set forth, e.g., 5 to 5,000 atoms of metal or metalloid ion per million silicon atoms, a range of to 2,000 atoms is preferred. Concentrations substantially below this range fail to provide a convenient brightness level under energization by readily obtainable means, and concentrations substantially above this level lead to decreased transparency in the product.

In the particular embodiment of this invention wherein the vitreous targets contains two or more metal or metalloid oxide luminescent activators, e.g., rare earth oxides, the concentration of each activator should be at least 5 atoms, preferably at least 50 atoms, with the total concentration of all the activators not exceeding 5,000 atoms, preferably less than 2,000 atoms.

The vitreous or noncrystalline silica compositions of this invention containing a rare earth oxide have been found to be both cathodoluminescent and photoluminescent; in particular, photoluminescence is obtained when the compositions are energized by ultraviolet rays. For example, in a specific embodiment of this invention, the glasses which contain lanthanum oxide or lanthanum oxide and an oxide of a rare earth selected from praseodymium, cerium, neodymium, samarium, europium, gadolinium, terbium, dysprosium, thulium, ytterbium, and lutetium, are cathodoluminescent, whereas those containing lanthanum oxide or lanthanum oxide and an oxide of a rare earth selected from praseodymium, cerium, neodymium, samarium, europium, gadolinium, terbium, dysprosium, thulium, and ytterbium are photoluminescent.

According to a further embodiment of the invention there are provided vitreous fibers of silica containing a luminescent activator, e.g., a rare earth oxide; and, optionally, at least another luminescent activator. In each of those embodiments pertaining to silica fibers, the broad and preferred concentration ranges are as stated hereinbefore.

In a further particular aspect of the invention there are provided glass fibers of the foregoing description wherein the central core of the fiber is as before described, but wherein there is an outer sheath of vitreous silica containing substantially no luminescent activator, or at least containing several orders of magnitude less luminescent activator than in the core.

The foregoing silica glass fibers containing luminescent activators are, of course, also responsive to the same energizing radiations as the bulk glasses, and can thus be used in various luminescence devices. However, the fibers containing the outer covering of vitreous silica cannot be used as cathodoluminescent fibers by bombardment through the silica sheath, since the electrons will not sufiiciently penetrate. However, they can be employed by bombardment on the end where the luminescent glass is exposed. The clad fibers, are, however, responsive to ultraviolet radiation, since silica will pass ultraviolet light through the sheath to the core.

According to a specific embodiment of this invention for preparing luminescent glass, there is provided a process for making a transparent, luminescent glass which comprises compacting a homogeneous mixture of finely divided vitreous silica and at least one rare earth oxide wherein the number of rare earth atoms per million silicon atoms is from 5 to 5,000, to form a coherent body, and heating the body thus obtained at 1,000 to 1,750 C. for a time of from about 1 minute to about 24 hours. ln a usual embodiment silica of particle size 1 to 5,000 millimicrons is used.

The time required to effect glass formation at a given temperature, or the temperature at a set time, decreases with decreased particle size. Also, homogeneous mixture of batch components is more assured when the silica particle size is small. Therefore, in a preferred embodiment, vitreous silica of particle size to 2,500 millimicrons is used. In a particularly preferred embodiment, vitreous silica of particle size 10 to 100 millimicrons is used.

Because the temperatures involved in the glass forming procedures of this invention are well below 1,800 C., the viscosity of the vitreous material remains high throughout; this prevents significant migration of the rate earth components, and favors their homogeneous distribution in the products already described.

The ability to obviate migration of rare earth components, during glass formation also allows formation of physically uniform glasses which contain a sharp boundary between two areas, one of which contains a rare earth not present in the other, by heating two or more pressed bodies of the type already described and which contain different rare earth components, while they are in contact, to form a glass. The boundary can be a plane, or any other shape to which the coherent bodies of this invention can be formed. The resultant glasses are useful as decorative materials since each sharply defined segment of, e.g., a rod, can contain a different rare earth or rare earths, and therefore emit a different luminescence emission when excited by energizing radiation. These materials are also useful in devices which require changing target materials rapidly or often.

Retention of high viscosities by the vitreous materials of this invention during formation of the glass bodies herein described also allows preparation of otherwise homogeneous vitreous bodies in which there is a sharp change in concentration of a constituent rare earth across a predetermined boundary, by heating two or more pressed bodies of the type already described and which contain different concentrations of the same rare earth component, while they are in contact, to form a glass. These products are especially useful in applications where luminescence emission of the same wavelength but varying intensity is desired.

The luminescent glass compositions of the present invention are useful as light sources in illuminating devices, signs, markers, etc. The luminescence devices of the present invention are useful as display means, Oscilloscopes, etc.

The starting material for the practice of the present invention is finely divided particulate noncrystalline or vitreous silica, usually with a maximum linear dimension of about 5,000 millimicrons. This material can be obtained by grinding or otherwise comminuting fused vitreous silica, or by combustion or vapor phase hydrolysis of silicon derivatives, particularly organosilanes and silicon halides. The latter process is preferable, particularly for the smaller particle range, because comminuting to obtain these sizes is laborious, and tends to introduce impurities. The particle size depends upon the heating schedule to be followed and the particular desired properties of the product. Limitations on the use of a certain particle size, temperature, and time to obtain a vitreous, transparent, luminescent product are best established by routine test, and cannot be set forth for all possible combinations.

Preliminary treatment of the particulate vitreous silica to remove water and organic impurities is conveniently carried out by heating at 700 C. for about 12 hours, followed by about 2 hours at 1,000 C., both steps optionally being carried out in a vacuum. Firing at 700 C. removes about 90 percent of the water and, if in air, organic material, firing at 1,000 C. removes most of the remaining water. Water thus removed is that which is present as chemisorbed water, i.e., as siliconbonded hydroxyl groups on the surface of the starting material. Although the anhydrous particulate silica thus obtained is subsequently contacted with water, as discussed below, rehydration by chemisorption is so slow that it does not take place under the conditions used; see A. C. Makrides and N. Hackerman, J. Phys. Chem. 63, 594 (1959).

The substantially anhydrous material obtained from the drying procedure is treated with about 10 ml. of water per gram of silica to obtain a slurry or paste which can be compacted. The liquid used neednot be water, since it is removed at a subsequent step, and serves merely as a medium in which to manipulate the silica; other liquids such as alcohol and acetone can be used with suitable modification of subsequent steps. The homogeneous addition of the small amounts of the oxide ingredient source to the silica is conveniently carried out at this step. The oxide source can be added in a form which is soluble in the liquid used, and subsequently precipitated in the paste, thereby assuring homogeneous distribution in the final product. When water is used to prepare the slurry, selected salts in aqueous solution can be added, and the oxide or hydroxide thereof precipitated by addition of base. The salt and precipitant should be selected so that byproducts from precipitation are volatilized during subsequent heating.

The paste thus obtained is next evaporated to dryness, at about C. or slightly more when water is the continuous phase, to give a more dense material than the original anhydrous powder. The compressed material is pulverized by any convenient means, usually by mortar and pestle or a ball mill. To retain highest purity, the abrasive surfaces should be of Alundum or silica. The pulverized material is fired at about 700 C. in air to remove organic impurities which may have been reintroduced since the initial purification, and to complete removal of the added water or other dispersing medium. Temperatures substantially above 700 C. should not be exceeded, since premature coalescence of the particles can occur. Usually about 30 minutes at 700 C. is adequate, with increasing time for larger quantities. The resultant dried powder is next treated with about two or three drops of water or other suitable liquid per gram to increase cohesion of the particles. The dampened powder is then formed by pressing, usually in a stainless steel or platinum mold for highest purity. Only about 100 p.s.i.g. is required for forming, although higher pressures can be used. Care should be taken that compacting is relatively uniform through the mass so the surface does not seal during subsequent firing, leaving bubbles in the interior of the body. The pressed forms can be left in the die during subsequent firing or removed if desired. The pressed forms are next subjected to temperatures of about 700 C. under a vacuum of about 10 mm. of mercury. The temperature is slowly increased to about 1,250 C., where it is maintained for about 30 to 60 minutes. The time at 1,250 C. depends upon the particular size used. In general, heating should be discontinued when the pressed form has shrunk about 40 percent along each linear dimension, and before the surface has a glazed appearance. The purpose of the vacuum is principally to avoid trapping bubbles and to keep the glass in its essentially anhydrous condition. The final coalescence is next carried out at temperatures up to l,750 C. in a vacuum conveniently maintained at about 10' mm. of mercury. The time required for complete coalescence varies with the temperature used, usually from about 24 hours at lower temperatures to about 3 minutes at temperatures near 1,750 C. The products thus obtained are vitreous, that is, they are substantially devoid of crystalline structure.

As used herein, the term substantially pure silica means silica which is at least 99 weight percent pure.

The silica used in the following examples had a particle size of 10 to 20 millimicrons and is designated Cab-O-Sil 0, and can be obtained from Godfrey L. Cabot, Inc., Boston 10, Mass; the manufacturer gives the composition on a total weight basis as:

Alp, 0.0 r 0% m0, 0.001% TiO 0.001% CuO-MgO 0.000% Nap 0.020% SiO, by difference 99.968%

The various aspects of the invention will now be illustrated with lanthanum oxide and it is to be understood that the other rare earth oxides can be used in place thereof as described and illustrated in the thirteen parent applications listed hereinbefore under RELATED applications. Likewise, other glass modifying ingredients may be substituted EXAMPLE 1 This example describes preparation of transparent, luminescent, silica glasses containing lanthanum oxide.

A. Vitreous silica of particle size 10 to 20 millimicrons was heated at 700 C. for 12 hours and then at 1,000 C. for about 2 hours. The material thus obtained was mixed with aqueous lanthanum nitrate in a ratio of 10 ml. of solution per gram of silica, and a solute concentration selected to provide 5 lanthanum atoms per million silicon atoms. Aqueous ammonia was added to precipitate lanthanum oxide on the surface of the silica, and the resultant mixture was evaporated to dryness at 100 C. The residue was ground with a mortar and pestle, and the powder thus obtained was first heated at 700 C. for 30 minutes, and then mixed with two drops of water per gram of solid. The resultant material was pressed in a platinum die at 100 p.s.i.g. to form a coherent cylinder about five-eighths inch in diameter and three-eighths inch high. The pressed form was dried at about 100 C., and then heated at 1,250 C. until the cylinder had shrunk about 40 percent along each linear dimension. The product thus obtained was placed in the closed end of a vitreous silica tube, whose interior was kept under vacuum, and this assembly was heated at 1,750 C. for 3 minutes, whereupon the silica tube collapsed around the cylinder as coalescence occurred to give a transparent, luminescent glass of silica and lanthanum oxide. The luminescent glass thus obtained is surrounded by an envelope of pure vitreous silica; the envelope is readily removed, if necessary, by grinding.

B. The procedure of example 1A was repeated, except that a concentration of 100 lanthanum atoms per million silicon atoms and a final coalescence temperature of l,600 C. for minutes were substituted for the conditions therein described; the product was a transparent, luminescent glass.

C. The procedure of example 1A was repeated, except that a concentration of 200 lanthanum atoms per million silicon atoms and a final coalescence temperature of l,500 C. for 40 minutes were substituted for the conditions therein described; the product was a transparent, luminescent glass.

D. The procedure of example 1A was repeated, except that a concentration of 2,000 lanthanum atoms per million silicon atoms and a final coalescence temperatures of l,400 C. for 9 hours were substituted for the conditions therein described; the product was a luminescent glass.

EXAMPLE 2 This example describes preparation of transparent, luminescent, silica glasses containing lanthanum oxide, and another rare earth oxide.

The procedure of example 1A was repeated, except that the aqueous lanthanum nitrate therein described was replaced with aqueous lanthanum nitrate and praseodymium nitrate in a concentration of solutes selected to provide l0 rare earth atoms per million silicon atoms; the product was a transparent, luminescent glass. The procedure of examples lA-D can also be adopted by suitable changes apparent to those skilled in the art to provide transparent, luminescent glasses of silica, lanthanum oxide and neodymium oxide; silica, lanthanum oxide, and samarium oxide; silica, lanthanum oxide, and europium oxide; silica, lanthanum oxide, and gadolinium oxide; silica, lanthanum oxide, and terbium oxide; silica, lanthanum oxide, and dysprosium oxide; silica, lanthanum oxide, and thulium oxide; silica, lanthanum oxide, and ytterbium oxide; and silica, lanthanum oxide, and lutetium oxide, wherein there are 100, 2,000, or 5,000 rare earth atoms per million silicon atoms and at least 5 lanthanum atoms per million silicon atoms.

EXAMPLE 3 This example describes preparation of luminescence devices from glasses made according to examples 1 and 2.

A. Samples of glasses prepared according to examples 1 and 2 were employed as target materials and irradiated with ultraviolet light filtered to obtain wavelengths of 2,537A. and 3,66OA. Under these conditions, glasses which contained lanthanum and optionally another rare earth gave the following results: lanthanum, weak green luminescence at the shorter wavelength; lanthanum-praseodymium, red luminescence of bright intensity at the shorter wavelength and infrared emission; lanthanum-neodymium, infrared emission; lanthanum-samarium, light pink luminescence of weak intensity at the shorter wavelength, blood red luminescence of weak intensity at the longer wavelength, and infrared emission; lanthanum-europium, light red luminescence of medium intensity at the shorter wavelength, pink luminescence of medium intensity at the longer wavelength, and infrared emission; lanthanum-gadolinium, ultraviolet emission; lanthanumterbium, light green luminescence of bright intensity at the shorter wavelength, and greenish luminescence of very weak intensity at the longer wavelength; lanthanum-dysprosium, light yellow luminescence of weak intensity at the shorter wavelength, yellow luminescence of very weak intensity at the longer wavelength, and infrared emission; lanthanum-thulium, dark blue luminescence of very weak intensity at the longer wavelength, and infrared emission; lanthanum-ytterbium, infrared emission.

B. Samples of glasses prepared according to examples 1 and 2 were employed as target materials and bombarded with cathode rays. Under these conditions, the glasses which contained lanthanum or lanthanum and another rare earth gave the following results: lanthanum, dark blue luminescence of weak intensity; lanthanum-praseodymium, dark red luminescence of medium intensity and infrared emission; lanthanum-neodymium, infrared emission; lanthanum-samarium, red luminescence of bright intensity and infrared emission; lanthanum-europium, orange luminescence of weak intensity and infrared emission; lanthanum-gadolinium, ultraviolet emission; lanthanum-terbium, blue green luminescence of very bright intensity; lanthanum-dysprosium, yellow luminescence of bright intensity, and infrared emission; lanthanum-thulium, dark blue luminescence of medium intensity, and infrared emission; lanthanum-ytterbium, infrared emission; lanthanum-lutetium, ultraviolet emission.

EXAMPLE 4 This example describes the preparation of a transparent, luminescent glass of silica and rare earth oxides, which possesses several boundaries on one side of each of which the glass contains a rare earth not present on the other side.

Vitreous silica of particle size 10 to 20 millimicrons was heated at 700 C. for 12 hours and then at 1,000 C. for about 2 hours. The material thus obtained was mixed with aqueous lanthanum nitrate in a ratio of 10 ml. of solution per gram of silica, and a solute concentration selected to provide lanthanum atoms per million silicon atoms. Aqueous ammonia was added to precipitate lanthanum oxide on the surface of the silica, and the resultant mixture was evaporated to dryness at 100 C. The residue was ground with a mortar and pestle, and the powder thus obtained was first mixed with two drops of water per gram of solid. The resultant material was pressed in a platinum die at 100 p.s.i.g. to form a coherent cylinder about five-eighths inch in diameter and three-eighths inch high, here designated sample A. The following samples were similarly prepared, substituting the designated rare earths for the lanthanum of sample A: sample B, 200 atoms of samarium per million silicon atoms; sample C, atoms of lutetium per million silicon atoms; sample D, 100 atoms of lanthanum and 100 atoms of praseodymium per million silicon atoms. The pressed form was dried at about 100 C., and then heated at l,250 C. until the cylinder had shrunk about 40 percent along each linear dimension. The samples thus obtained were stacked inalphabetical order in a vitreous silica tube, and the tube, whose interior was kept under vacuum, was heated at 1,750 C. for 3 minutes, whereupon the silica tube collapsed EXAMPLE This example describes the preparation of a transparent, luminescent glass of silica containing lanthanum oxide, which possesses several boundaries on one side of which the concentration of lanthanum is different from that on the other side.

By the procedure of example 4, a series of five samples was prepared containing, respectively, 5, 100, 200, 300, and 400 lanthanum atoms per million silicon atoms. The resultant samples were coalesced as described in the cited example to give a transparent, luminescent glass which was physically homogeneous and had sharp boundaries between successive regions containing lanthanum in the cited concentrations.

In particular, the luminescence spectra of the silicalanthanum oxide glasses of this invention show a broad continuum from about 400 to about 520 nm. (nanometers). The spectra of the silica glasses of this invention which contain lanthanum oxide and other rare earth oxide display this continuum and, superimposed thereon, maxima at the following principal wavelengths; the term in parentheses is an approxi mation of relative intensity: lanthanum-praseodymium 10.9 nm. (medium), 910 nm. (strong), 860 nm. (strong), 722 nm. (weak), 708 nm. (weak), 656 nm. (strong), 635 nm. (strong), 612 nm. (strong), 592 nm. (weak), 490 nm. (weak); lanthanum-neodymium, 890 nm. (strong), 907 nm. (medium), 1,010 nm. (weak); lanthanum-samarium, 566 nm. (strong), 578 nm. (weak), 605 nm. (strong), 651 nm. (strong), 663 nm. (medium); lanthanum-europium 617 nm. (strong), 629 nm. (medium), 657 nm. (medium), 700 nm. (weak); lanthanum-gadolinium 325 nm. (weak), 316 nm. (strong), 314 nm. (strong), 313 nm. (medium), 311 nm., 308 nm., 306 nm. (weak); lanthanum-terbium 377 nm., 381 nm., 383 nm., 413 nm., 416 nm., 420 nm., 437 nm., 440 nm., 443 nm., 459 nm., 474 nm., 486 nm., 541 nm., 548 nm., 595 nm., 630 nm., 653 nm., lanthanum-dysprosium 582 nm., 602 nm. (strong), 669 nm., 671 nm., 678 nm. (medium), 758 nm. (strong), 870 nm. (weak); lanthanum-thulium 458 nm., 461 nm., 464 nm. (strong), 787 nm.; lanthanum-ytterbium 986 nm. (medium), 1,040 nm. (weak); lanthanum-lutetium ca. 450 nm.

EXAMPLE 6 A. The procedure of example 1A was repeated, except that praseodymium nitrate, neodymium nitrate, samarium nitrate, gadolinium nitrate, europium nitrate, terbium nitrate, dysprosium nitrate, holmium nitrate, erbium nitrate, thulium nitrate, ytterbium nitrate, or lutetium nitrate was used in place of the lanthanum nitrate. A transparent, luminescent glass of silica and the rare earth oxide was formed in each instance. The luminescent glass thus obtained is surrounded by an envelope of pure vitreous silica; the envelope is readily removed, if necessary, by grinding.

B. The procedure of example 6A was repeated except that a concentration of 100 of the aforesaid rare earth oxides per million silicon atoms and a final coalescence temperature of l,600 C. for 10 minutes were substituted for the conditions therein described; the product was a transparent, luminescent glass.

C. The procedure of example 6A was repeated, except that a concentration of 200 of the aforesaid rare earth oxides per million silicon atoms and a final coalescence temperature of 1,500 C. for 40 minutes were substituted for the conditions therein described. The product was a transparent, luminescent glass.

D. The procedure of example 6A was repeated, except that a concentration of 2,000 of the aforesaid rare earth oxides per million silicon atoms and a final coalescence temperature of 1,400 c. for 9 hours we substituted for the conditions therein described. The product was a luminescent glass.

EXAMPLE 7 The procedure of example 1A was repeated for each of the following aqueous mixtures which were substituted for the aqueous lanthanum nitrate, and a transparent, luminescent silica glass was obtained in each instance; praseodymium nitrate and neodynium nitrate; neodynium nitrate and samarium nitrate; samarium nitrate and europium nitrate; europium nitrate and gadolinium nitrate; gadolinium nitrate and terbium nitrate; terbium nitrate and dysprosium nitrate; disprosium nitrate and holmium nitrate; holmium nitrate and thulium nitrate; erbium nitrate and thulium nitrate; thulium nitrate and ytterbium nitrate; ytterbium nitrate and lutetium nitrate. The concentration of solutes was selected to provide 10 rare earth atoms per million silicon atoms. The product was a transparent luminescent glass.

The procedure of examples lA-lD can also be adapted by suitable changes apparent to those skilled in the art to provide transparent, luminescent glasses of silica plus at least two of the aforesaid rare earth oxides.

EXAMPLE 8 A. Samples of glasses prepared according to examples 6 and 7 were employed as target materials and irradiated with ultraviolet light filtered to obtain wavelengths of 2,537A. and 3,660A. Various results were noted, depending upon the particular rare earth oxides present in the glass.

B. Samples of glasses prepared according to examples 6 and 7 were employed as target materials and bombarded with cathode rays. Again, different results were noted with respect to each glass, depending upon the composition thereof.

The silica glasses of this invention which contain praseodymium oxide and gadolinium oxide possess remarkable and unexpected properties. When these glasses are excited with ultraviolet radiation of wavelength 2,537A., the emission spectrum of gadolinium is markedly enhanced. Quantitative intensity measurements are difficult, but it is estimated that the presence of praseodymium multiplies the intensity of gadolinium luminescence by at least a factor of five. FIG. 1 shows a trace which compares the spectra obtained from glasses which contain gadolinium but not praseodymium (lower curve) and glasses which contain gadolinium and praseodymium (upper curve). The ordinate is proportionate to intensity of emission under the same concentrations and excitation conditions for each glass; it is apparent that the presence of praseodymium causes substantial increase in brightness of luminescence emission. The cause of this synergistic enhancement of gadolinium emission by praseodymium is unknown.

The present invention also provides new, substantially homogeneous glasses of silica containing europium oxide and terbium oxide which possess remarkable and unexpected selective enhancement of the luminescence from certain electronic energy levels in terbium. Thus according to this aspect of the invention, addition of terbium and adjustment of the europium and terbium concentrations of the silica glasses heretofore described can be used to enhance selectively certain wavelengths of terbium emission while others are substantially unaffected, and emission from europium is decreased. The causes of this behavior are unknown. A suitable rare earth concentration range for the silica glasses of this invention containing terbium oxide and europium oxide is from about 5 to about 5,000 rare earth atoms per million silicon atoms, and at least 5 europium atoms per million silicon atoms.

The unusual and unexpected enhancement of certain terbium emission wavelengths in the presence of europium is shown in FIG. 2, which is a trace of the luminescence spectrum of a glass of this invention containing 2,000 terbium atoms and 200 europium atoms per million silicon atoms, excited by 3,660A. ultraviolet irradiation; abscissa units are nanometers. Since neither glasses containing europium but not terbium, nor those containing terbium but not europium gave measurable spectra under similar excitation conditions, it is apparent that a marked and unexpected enhancement of luminescence is provided by glasses containing both of these rare earths. The causes of this synergistic effect are unknown.

The present invention also provides new, substantially homogeneous glasses of silica containing europium oxide and lutetium oxide which are remarkable and unexpected in that they possess luminescence emission spectra of unusual and unpredictable wavelengths and intensities. Thus, according to this aspect of the invention, addition of lutetium and europium can be used to provide a silica glass containing europium oxide and lutetium oxide which shows under suitable excitation a broad emission continuum of high intensity from about 400 nm. to about 650 nm. (nanometers); this type of emission is not characteristic of either europium or lutetium in the absence of one another. The causes of this synergistic effect are unknown.

The unusual and unexpected spectra characteristic of the silica glasses of this invention containing europium and lutetium are represented in H0. 3, which is a trace of the luminescence spectrum of a glass of this invention containing 100 europium atoms and 100 lutetium atoms per million silicon atoms, excited by 3,660A. ultraviolet irradiation; abscissa units are nanometers. Since neither glasses containing europium but not lutetium, nor those containing lutetium but not europium gave measurable spectra under similar excitation conditions, it is apparent that a marked and unexpected enhancement of luminescence is provided by glasses containing both of these rare earths. Also, the shape of the curve is not attributable to either rare earth. The causes of this synergistic effect are unknown.

The present invention also provides new, substantially homogeneous glasses of silica containing terbium oxide and cerium oxide which possess remarkable and unexpected selective enhancement of the luminescence from certain electronic energy levels in terbium. Thus according to this aspect of the invention, addition of cerium and adjustment of the cerium and terbium concentrations of the silica glasses heretofore described can be used to enhance selectively certain wavelengths of terbium emission while others are substantially unaffected, and emission from cerium is decreased. The causes of this behavior are unknown. A suitable rare earth concentration range for the silica glasses of this invention containing terbium oxide and cerium oxide is from about to about 5,000 rare earth atoms per million silicon atoms, and at least 5 terbium atoms per million silicon atoms.

The unusual and unexpected enhancement of certain terbium emission wavelengths in the presence of cerium is shown in FIG. 4, which is a composite trace of the luminescence spectrum of a silica glass containing 200 cerium atoms per million silicon atoms, (lower curve), and the spectrum of a silica glass containing 200 terbium atoms and 200 cerium atoms per million silicon atoms (upper curve) excited'by 3,660A. ultraviolet radiation; the abscissa units are nanometers. Terbium under similar excitation shows no spectrum when similarly measured, and as FIG. 4 shows, cerium in the absence of terbium shows relatively weak intensity luminescence, whereas glasses containing both show the relatively bright intensity spectrum characteristic of terbium shown as the upper trace in FIG. 4. The causes of this synergistic effect are unknown.

In particular, these principal wavelengths were observed in luminescence of the silica glasses of this invention containing oxides of the following rare earths; nm. represents nanometers, and the term in parentheses is an approximation of relative intensity: terbium, 377 nm., 381 nm., 383 nm., 413 nm., 416 nm., 420 nm., 437 nm., 440 nm., 443 nm., 459 nm., 474 nm., 486 nm., 541 nm., 548 nm., 595 nm., 630 nm., 653 nm.; terbium-dysprosium, 582 nm., 602 nm., (strong), 669 nm., 671 nm., 678 nm., (medium), 758 nm., (strong), 870 nm. (weak), 377 nm., 381 nm., 383 nm., 413 nm., 416 nm., 420 nm.. 437 nm., 440 nm., 443 nm., 459 nm., 474 nm., 486 nm.,

541 nm., 548 nm., 595 nm., 630 nm., 653 nm.; terbium-holmium, 377 nm., 381 nm., 383 nm., 413 nm., 416 nm., 420 nm., 437 nm., 440 nm., 443 nm., 459 nm., 474 nm., 486 nm., 541 nm., 548 nm., 595 nm., 630 nm., 653 nm.; terbium-erbium, 377 nm., 381 nm., 383 nm., 413 nm., 416 nm., 420 nm., 437 nm., 44 nm., 443 nm., 459 nm., 474 nm., 486 nm., 541 nm., 548 nm., 595 nm., 630 nm., 653 nm.; terbium-thulium, 458 nm., 461 nm., 464 nm. (strong), 787 nm., 377 nm., 381 nm., 383 nm., 413 nm., 416 nm., 420 nm., 437 nm., 440 nm., 443 nm., 459 nm., 474 nm., 486 nm., 541 nm., 548 nm., 595 nm., 630 nm., 653 nm.; terbium-ytterbium, 986 nm. (medium), 1,040 nm. (weak), 377 nm., 381 nm., 383 nm., 413 nm., 416 nm., 420 nm., 437 nm., 440 nm., 443 nm., 459 nm., 474 nm., 486 nm., 541 nm., 548 nm., 595 nm., 630 nm., 653 nm.; terbium-lutetium, ca. 450 nm., 377 nm., 381 nm., 383 nm., 413 nm., 416 nm., 420 nm., 437 nm., 440 nm., 443 nm., 459 nm., 474 nm., 486 nm.,541nm., 548 nm., 595 nm., 630 nm., 653

EXAMPLE 9 This example describes preparation of transparent, luminescent silica glasses containing terbium oxide and cerium oxide, and their use as luminescence targets.

The procedure of example 6A was repeated, except that the aqueous terbium nitrate therein described was replaced with aqueous terbium nitrate and cerium nitrate in a concentration of solutes selected to provide 10 rare earth atoms per million silicon atoms; the product was a transparent, luminescent glass. The procedure of examples 6A-D can also be adopted by suitable changes apparent to those skilled in the art to provide transparent, luminescent glasses of silica containing terbium and cerium oxides, wherein the number of rare earth atoms per million silicon atoms is from 5 to 5,000, and the number of terbium atoms per million silicon atoms is at least 5. The glasses thus obtained show cathodoluminescence and photoluminescence: when bombarded with cathode rays they show light blue luminescence of medium intensity; when bombarded with 2,537A. ultraviolet radiation they show light blue luminescence of medium intensity; when bombarded with 3,660A. ultraviolet radiation they show light blue luminescence of bright intensity. Fibers drawn from these glasses by conventional means gave similar results. In particular, luminescence spectra of these glasses show an underlying continuum from about 410 nm. to about 600 nm., attributable to cerium, with superimposed maxima at 377 nm., 381 nm., 383 nm., 413 nm., 416 nm., 420 nm., 437 nm., 440 nm., 443nm., 459 nm., 474 nm., 486 nm., 541 nm., 548 nm., 595 nm., 630 nm., and 653 nm., attributable to terbium.

As previously discussed, spectra of these glasses compared with those of silica glasses similarly prepared but containing terbium but not cerium or cerium but not terbium at the same concentrations show decreased intensity of luminescence attributable to cerium and an increased intensity of certain wavelengths attributable to terbium, in particular the maxima at 486 nm., 541 nm., 548 nm., 595 nm., 630 nm., and 653 nm.

Although the examples hereof have been directed toward the use of certain rare earth oxides, it will be obvious to those skilled in the art that other rare earth oxide combinations can be used as well as other oxide ingredients, e.g., metal or metalloid oxides, including both luminescent and nonluminescent activators.

The particular nonluminescent activator will depend upon the specific glass characteristics desired. Thus if one selects an oxide of cobalt (alone or in combination with other oxide ingredients), the resulting glass (prepared in accordance with this invention) will have high-temperature stability, low-thermal expansion, unique filter properties, and unique sonic properties (for use in delay lines).

ln preparing the mixture of silica and the oxide ingredient(s), the oxide may be used or it may be prepared by oxidation or hydrolysis as described hereinbefore. When the latter technique is used, any source of the oxide cation can be used providing such source can be dissolved in a liquid suitablefor wetting colloidal or otherwise finely divided silica and subsequently precipitated onto the silica where it can be made to remain during the sintering and coalescing steps of the process without objectionable chemical changes, e.g., such as the release of gas due to a change of valence.

It will be evident that modifications of this invention can be made without departing from the spirit and scope of this disclosure or the scope of the following claims.

We claim:

l..ln a luminescence device having a source of energizing rays and a target for the conversion of the rays to luminescent emission, the improvement wherein the target is an essentially transparent, homogeneous silica glass consisting essentially of silica and at least one rare earth oxide selected from the group consisting of praseodymium, neodymium, samarium, europium, gadolinium, terbium, dysprosium, erbium, thulium and ytterbium oxides, the number of rare earth atoms per million atoms of silicon ranging from about to about 5,000, said silica glass, exclusive of said rare earth oxides, being at least 99 weight percent silica.

2. The improvement of claim 1 wherein said at least one rare earth oxide is an oxide selected from the group consisting of oxides of praseodymium, neodymium, samarium, europium, gadolinium, terbium, dysprosium, erbium, thulium, and ytterbium in combination with at least one different rare earth oxide selected from the group consisting of oxides of lanthanum, cerium, praseodymium, neodymium, samarium, europium, gadolinium, terbium, dysprosium, erbium, thulium, ytterbium, lutetium, and holmium.

3. In a photoluminescence device having a source of energizing rays and a target for the conversion of the rays to luminescent emission, the improvement wherein the target is an essentially transparent, homogeneous silica glass consisting essentially of silica and at least one rare earth oxide selected from the group consisting of praseodymium, neodymium, samarium, europium, gadolinium, terbium, dysprosium, erbium, thulium and ytterbium oxides, the number of rare earth atoms per million atoms of silicon ranging from about 5 to about 5,000, said silica glass, exclusive of said rare earth oxides, being at least 99 weight percent silica.

4. In a cathodoluminescence device having a source of energizing rays and a target for the conversion of the rays to luminescent emission, the improvement wherein the target is an essentially transparent, homogeneous silica glass consisting essentially of silica and at least one rare earth oxide selected from the group consisting of praseodymium, neodymium, samarium, europium, gadolinium, terbium, dysprosium, erbium, thulium and ytterbium oxides, the number of rare earth atoms per million atoms of silicon ranging from about 5 to about 5,000, said silica glass, exclusive of said rare earth oxides, being at least 99 weight percent silica.

5. The improvement of claim 4 wherein the source of energizing rays is a source of cathode rays and the target is a face plate of a cathode-ray tube.

6. In a process for generating luminescence emission by causing energizing radiation to impinge on a target, the improvement wherein the target is an essentially transparent, homogeneous silica glass consisting essentially of silica and at least one rare earth oxide selected from the group consisting of praseodymium, neodymium, samarium, europium, gadolinium, terbium, dysprosium, erbium, thulium and ytterbium oxides, the number of rare earth atoms per million atoms of silicon ranging from about 5 to about 5,000, said silica glass, exclusive of said rare earth oxides, being at least 99 weight percent silica.

7. In a process for generating luminescence emission by causing cathode rays to impinge on a target, the improvement wherein the target is an essentially transparent, homogeneous silica glass consisting essentially of silica and at least one rare earth oxide selected from the group consisting of praseodymium, neodymium, samarium, europium, gadolinium, terbium,

dysprosium, erbium, thulium and ytterbium oxides, the number of rare earth atoms per million atoms of silicon ranging from about 5 to about 5,000, said silica glass, exclusive of said rare earth oxides, being at least 99 weight percent silica,

8. In a process for generating luminescence emission by causing ultraviolet light rays to impinge on a target, the improvement wherein the target is an essentially transparent, homogeneous silica glass consisting essentially of silica and at least one rare earth oxide selected from the group consisting of praseodymium, neodymium, samarium, europium, gadolinium, terbium, dysprosium, erbium, thulium and ytterbium oxides, the number of rare earth atoms per million atoms of silicon ranging from about 5 to about 5,000, said silica glass, exclusive of said rare earth oxides, being at least 99 weight percent silica.

9. In a luminescence device having a source of energizing radiation and a target for conversion of said rays to luminescent emission, the improvement wherein said target is a homogeneous silica glass consisting essentially of silica and oxides of the rare earths praseodymium and gadolinium wherein the total number of such rare earth atoms per million silicon atoms is from 10 to 5,000 and the number of each of said rare earth atoms per million silicon atoms is at least 5, said silica glass, exclusive of said rare earth oxides, being at least 99 weight percent silica.

10. in a luminescence device having a source of energizing radiation and a target for conversion of said rays to luminescent emission, the improvement wherein said target is a homogeneous silica glass consisting essentially of silica and oxides of the rare earths terbium and europium wherein the total number of such rare earth atoms per million silicon atoms is from 10 to 5,000 and the number of each of said rare earth atoms per million silicon atoms is at least 5, said silica glass, exclusive of said rare earth oxides, being at least 99 weight percent silica.

11. In a luminescence device having a source of energizing radiation and a target for conversion of said rays to luminescent emission, the improvement wherein said target is a homogeneous silica glass consisting essentially of silica and oxides of the rare earths europium and lutetium wherein the total number of such rare earth atoms per million silicon atoms is from 10 to 5,000 and the number of each of said rare earth atoms per million silicon atoms is at least 5, said silica glass, exclusive of said rare earth oxides, being at least 99 weight percent silica.

12. in a luminescence device having a source of energizing radiation and a target for conversion of said rays to luminescent emission, the improvement wherein said target is a homogeneous silica glass consisting essentially of silica and oxides of the rare earths terbium and cerium wherein the total number of such rare earth atoms per million silicon atoms is from 10 to 5,000 and the number of each of said rare earth atoms per million silicon atoms is at least 5, said silica glass, exclusive of said rare earth oxides, being at least 99 weight percent silica.

PflIN I bK'S TRIM L Patent No. 3.634,?ll v Dated January 11 1972 Inventor(s) Stephen W. Barber and William F. Nelson It is certified that error appears in the above-identified patent and that said Letters Patent are hereby corrected as shown below:

In the title page in block ['73:], the material after "Owens-Illinois, Inc," should read:

--Division of'Ser, No. 841,690, July 1, 1969, now Patent No. 3,527,?11, which is a continuation of Ser. No.

641,624, May 25, 1967, now abandoned, which in turn was a continuation-in-part of Ser. No. 355,444; Ser- No. 355,253; Ser. N0 355,407; Ser, No, 355,469;

v 1 Ser, No. 355,445; Ser, No, 355,251; Ser. No. 355,408;

, 4 Ser. No. 355,470; Ser. No 355,421; Ser, No, 355,248;

' Sera No. 355,409; Ser No. 355,471; Ser, No. 355,422,

a all of Mar. 2'7, 1964, all now abandoned. This application Jan, 11, 1972, Ser, No. 41,455"- The heading at the top of Column 1 "RELATED APPLICATION" should read -RELATED APPLICATIONS--.,

The period should be deleted from the end of the first paraph of Column 1 and the following inserted therefor which is a continuation of Ser No, 641,624, filed May 25, 1967, now abandoned, which in turn was a continuation-in-part of the following applications:

Serial No Filed 355,444 March 27 1964, now abandoned 355,253 March 2'? 1964, now abandoned 355,407 March 27 1964, now abandoned 355,469 March 27 1964, now abandoned 355,445 5 March 2'7 1964, now abandoned Page 1 of 2 E FORM PO-IOSO (10-69) USCOMM DC M76436? U-S. ,GOVERNMENY PRINTING OFFICE: ISI 0-366-334,

Patent No. 3 631 5711 Serial No;

(SEAL) Attest:

MQCQY M. GIBSON JR. Attesting Officer Dated Filed January 11 UNITEDSimT S 'RATENT OFFICE page 2 of 2 CERTIFICATE 0F CORRECTION Inventor(s) Stephen W. Barber and Williav .3. Nelson It is certified that error appears in the above-identified patent and that said Letters Patent are hereby corrected as shown below:

March March March March March March March March now DOW

HOW

DOW

HOW

now

now

now

196% 196% 196A, 196A, 1964,- 196a, 196M, 196M,

Signed and sealed this 12th day of November 1974.

C. MARSHALL DANN Commissioner of Patents F ORM O-i050 (10-69) US GOVERNMENT PRINTING OFFICE: I969 0-166-33.

USCOMM'DC 60376-1 60 

2. The improvement of claim 1 wherein said at least one rare earth oxide is an oxide selected from the group consisting of oxides of praseodymium, neodymium, samarium, europium, gadolinium, terbium, dysprosium, erbium, thulium, and ytterbium in combination with at least one different rare earth oxide selected from the group consisting of oxides of lanthanum, cerium, praseodymium, neodymium, samarium, europium, gadolinium, terbium, dysprosium, erbium, thulium, ytterbium, lutetium, and holmium.
 3. In a photoluminescence device having a source of energizing rays and a target for the conversion of the rays to luminescent emission, the improvement wherein the target is an essentially transparent, homogeneous silica glass consisting essentially of silica and at least one rare earth oxide selected from the group consisting of praseodymium, neodymium, samarium, europium, gadolinium, terbium, dysprosium, erbium, thulium and ytterbium oxides, the number of rare earth atoms per million atoms of silicon ranging from about 5 to about 5,000, said silica glass, exclusive of said rare earth oxides, being at least 99 weight percent silica.
 4. In a cathodoluminescence device having a source of energizing rays and a target for the conversion of the rays to luminescent emission, the improvement wherein the target is an essentially transparent, homogeneous silica glass consisting essentially of silica and at least one rare eaRth oxide selected from the group consisting of praseodymium, neodymium, samarium, europium, gadolinium, terbium, dysprosium, erbium, thulium and ytterbium oxides, the number of rare earth atoms per million atoms of silicon ranging from about 5 to about 5,000, said silica glass, exclusive of said rare earth oxides, being at least 99 weight percent silica.
 5. The improvement of claim 4 wherein the source of energizing rays is a source of cathode rays and the target is a face plate of a cathode-ray tube.
 6. In a process for generating luminescence emission by causing energizing radiation to impinge on a target, the improvement wherein the target is an essentially transparent, homogeneous silica glass consisting essentially of silica and at least one rare earth oxide selected from the group consisting of praseodymium, neodymium, samarium, europium, gadolinium, terbium, dysprosium, erbium, thulium and ytterbium oxides, the number of rare earth atoms per million atoms of silicon ranging from about 5 to about 5,000, said silica glass, exclusive of said rare earth oxides, being at least 99 weight percent silica.
 7. In a process for generating luminescence emission by causing cathode rays to impinge on a target, the improvement wherein the target is an essentially transparent, homogeneous silica glass consisting essentially of silica and at least one rare earth oxide selected from the group consisting of praseodymium, neodymium, samarium, europium, gadolinium, terbium, dysprosium, erbium, thulium and ytterbium oxides, the number of rare earth atoms per million atoms of silicon ranging from about 5 to about 5,000, said silica glass, exclusive of said rare earth oxides, being at least 99 weight percent silica.
 8. In a process for generating luminescence emission by causing ultraviolet light rays to impinge on a target, the improvement wherein the target is an essentially transparent, homogeneous silica glass consisting essentially of silica and at least one rare earth oxide selected from the group consisting of praseodymium, neodymium, samarium, europium, gadolinium, terbium, dysprosium, erbium, thulium and ytterbium oxides, the number of rare earth atoms per million atoms of silicon ranging from about 5 to about 5,000, said silica glass, exclusive of said rare earth oxides, being at least 99 weight percent silica.
 9. In a luminescence device having a source of energizing radiation and a target for conversion of said rays to luminescent emission, the improvement wherein said target is a homogeneous silica glass consisting essentially of silica and oxides of the rare earths praseodymium and gadolinium wherein the total number of such rare earth atoms per million silicon atoms is from 10 to 5,000 and the number of each of said rare earth atoms per million silicon atoms is at least 5, said silica glass, exclusive of said rare earth oxides, being at least 99 weight percent silica.
 10. In a luminescence device having a source of energizing radiation and a target for conversion of said rays to luminescent emission, the improvement wherein said target is a homogeneous silica glass consisting essentially of silica and oxides of the rare earths terbium and europium wherein the total number of such rare earth atoms per million silicon atoms is from 10 to 5,000 and the number of each of said rare earth atoms per million silicon atoms is at least 5, said silica glass, exclusive of said rare earth oxides, being at least 99 weight percent silica.
 11. In a luminescence device having a source of energizing radiation and a target for conversion of said rays to luminescent emission, the improvement wherein said target is a homogeneous silica glass consisting essentially of silica and oxides of the rare earths europium and lutetium wherein the total number of such rare earth atoms per million silicon atoms is from 10 to 5, 000 and the number of each of sAid rare earth atoms per million silicon atoms is at least 5, said silica glass, exclusive of said rare earth oxides, being at least 99 weight percent silica.
 12. In a luminescence device having a source of energizing radiation and a target for conversion of said rays to luminescent emission, the improvement wherein said target is a homogeneous silica glass consisting essentially of silica and oxides of the rare earths terbium and cerium wherein the total number of such rare earth atoms per million silicon atoms is from 10 to 5,000 and the number of each of said rare earth atoms per million silicon atoms is at least 5, said silica glass, exclusive of said rare earth oxides, being at least 99 weight percent silica. 